US4105609A - Deactivation of catalysts of the ziegler type used for the preparation of polyethylene in high pressure, high temperature processes - Google Patents

Deactivation of catalysts of the ziegler type used for the preparation of polyethylene in high pressure, high temperature processes Download PDF

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Publication number
US4105609A
US4105609A US05/661,414 US66141476A US4105609A US 4105609 A US4105609 A US 4105609A US 66141476 A US66141476 A US 66141476A US 4105609 A US4105609 A US 4105609A
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salt
reaction mixture
injected
catalyst
reactor
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US05/661,414
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Jean-Pierre Machon
Bernard Levresse
Pierre Gloriod
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Norsolor SA
Vitafin NV
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Chimique des Charbonnages SA
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Assigned to NORSOLOR, SOCIETE ANONYME reassignment NORSOLOR, SOCIETE ANONYME ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: SOCIETE CHIMIQUE DES CHARBONNAGES, SOCIETE ANONYME
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F6/00—Post-polymerisation treatments
    • C08F6/02—Neutralisation of the polymerisation mass, e.g. killing the catalyst also removal of catalyst residues
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02—Ethene

Definitions

  • the present invention relates to an improved process for the preparation of polyethylene in accordance with the high pressure, high temperature processes which use a catalyst of the ZIEGLER type.
  • the conventional processes for the polymerisation and copolymerisation of ethylene under high pressures and at high temperatures are carried out at pressures above 500 bars and at temperatures above about 160° C, using known catalysts.
  • the reaction mixture On leaving the high pressure reactor (in which the polymerisation reactions have been carried out) the reaction mixture is let down in at least one separator in which the working conditions are chosen so as to separate the ethylene (and, where relevant, the other monomers) in one or more stages from the polymer which has formed in the reactor.
  • the pressure in this first separator in below 500 bars.
  • the working conditions (temperature, pressure and residence time) in the said separator(s) may be such that the polymerisation (or copolymerisation) of the monomer (or monomers) can continue and give rise to undesirable products (for example low molecular weight products, waxes and the like), the formation of which it is desirable to avoid.
  • the present invention relates to a process for avoiding such disadvantages.
  • the present invention relates to an improved process for the polymerisation and copolymerisation of ethylene, under a pressure above 500 bars and at temperatures above about 160° C, in the presence of catalysts comprising a transition metal derivative and an alkyl-aluminium.
  • This process aims to avoid the secondary reactions which might develop in the separator(s) and is characterised in that at the end of the reaction at least one product selected from alkali metal salts and alkaline earth metal salts of carboxylic acids is injected into the reaction mixture, the amount injected being sufficient to bring about the deactivation of the catalyst.
  • the said alkali metal salt or alkaline earth metal salt must be so chosen that the products which it could form with the constituents of the catalyst (titanium derivatives and aluminium derivatives) are inert and are not carried with the monomer (ethylene) during recirculation. According to the invention, the products obtained as a result of the action of the metal salt on the constituents of the catalyst remain in the finished polymer.
  • the transition metal derivative which can be used as a constituent of the polymerisation catalyst is generally a titanium derivative and more particularly titanium trichloride which can optionally contain co-crystallised aluminium chloride.
  • the alkyl-aluminium which can be used as the other constituent of the catalyst is preferably a trialkyl-aluminium, a dialkyl-aluminium monohalide or a pentalkylsilox alane.
  • 2,027,788 and consisting of an activated solid obtained by reacting a halogen derivative of a transition metal (for example TiCl 4 ) with a compound of the formula Xm-nM(OR) n and an organo-metallic compound of the aluminium-alkyl type are to be considered as catalysts of the Ziegler type which can be used in accordance with the invention.
  • a halogen derivative of a transition metal for example TiCl 4
  • a compound of the formula Xm-nM(OR) n and an organo-metallic compound of the aluminium-alkyl type are to be considered as catalysts of the Ziegler type which can be used in accordance with the invention.
  • the proportions of the catalyst constituents are such that the atomic ratio (Al/Ti) is substantially between 1 and 10.
  • the process according to the invention is applicable to the polymerisation of ethylene and the copolymerisation of ethylene with other monomers which are copolymerisable with ethylene in the presence of catalysts of this type; these comonomers are, for example, alpha-olefins such as propylene, butene-1 and the like.
  • the ethylene polymerisation or copolymerisation reaction can be carried out in stirred autoclave reactors or in tubular reactors or in series of reactors of either the autoclave type, or the tubular type; in all cases, however, the working conditions are such that the reaction medium is homogeneous, i. e. the polymer is soluble in the reaction mixture.
  • this polymerisation reaction it is of course possible to use known processes for regulating the molecular weight of the polymers (e. g. injection of suitable transfer agents) or for improving the properties of the resulting products (e. g. injection of antioxidants or similar additives into the polymerisation reactor or at the outlet from the latter).
  • the polymerisation or copolymerisation reaction according to the invention is carried out continuously. Therefore the metal salt(s) must be injected into the reaction mixture at the point of the installation where it is considered that the polymerisation or copolymerisation reaction must be stopped.
  • This point of the installation may be located in a zone of the reactor close to the outlet from the latter or in one of the separators in which the reaction mixture leaving the reactor is collected. In general, it is preferred that the material should be injected as close as possible to the reactor outlet valve.
  • the amount of metal salt injected must be sufficient to ensure deactivation of the catalyst. This deactivation is effected by destruction of at least one of the constituents of the catalyst, namely the transition metal derivative and the alkyl-aluminium. However, it is preferable to use sufficient metal salt for both of the constituents of the catalyst to react with the said salt. According to the invention, the amount of salt used is preferably such that the ratio of milliequivalent-grams of the metal in the said salt to milliatoms of aluminium and titanium contained in the catalyst is substantially between 0.4 and 8.
  • alkali metal salts and alkaline earth metal salts of the carboxylic acids which can be used according to the invention, there should preferably be mentioned the alkali metal salts and alkaline earth metal salts of saturated fatty acids and of aromatic acids, such as, for example, sodium stearate, potassium stearate, calcium stearate, magnesium stearate, sodium benzoate, potassium benzoate, sodium naphthenate and potassium naphthenate. All these salts can be injected either in the pure (molten) state or in suspension or in solution in an hydrocarbon.
  • a high pressure (1,500 bars) ethylene polymerisation line comprising a reactor of the stirred autoclave type, the volume of which is 5 liters, and two separators in series, the first of which operates at a pressure of 250 bars and the second at a pressure of 15 bars;
  • the reaction temperature is of the order of 260° C and the mean temperature in the separators is 260° to 270° C;
  • the average residence time of the ethylene in the reactor is 50 seconds;
  • the catalyst used consists of violet titanium trichloride (in the form of a co-crystallised product of the formula TiCl 3 .1/3 AlCl 3 ) and of tributyl-aluminium, the atomic ratio Al/Ti being between 1 and 5; about 1% of hydrogen, acting as a transfer agent, was injected into the reactor.
  • the metal salt (agent for destroying the catalyst) is injected into the reactor just before the extrusion valve.
  • the density of the polyethylene expressed in g/cm 3 , this being measured at 20° C on products which have been reheated for 1 hour at 150° C and been cooled at a speed of 50° C/hour;
  • melt index measured in accordance with standard specification ASTM 1238-62 at a temperature of 190° C and with a load of 2.16 kg;
  • the polydispersity index which is the ratio Mw/Mn of the weight average molecular weight to the number average molecular weight as defined in "Polythene", Renfrew & Morgan (1957) p. 90;
  • catalyst residues namely Al, Ti and alkali metal or alkaline earth metal (M) expressed in ppm;
  • Reactor pressure 1,500 bars.
  • Average residence time 35 seconds.
  • Catalyst system TiCl 3 .1/3AlCl 3 - AlBu 3 .
  • the temperature of the separator was different in each experiment.
  • the metal salt (destroying agent) is injected into the reactor just before the extrusion valve.
  • melt index (M.I.) of the polyethylene measured as above;
  • Table IIbis gives the feed rate of the titanium constituent of the catalyst (in milliatoms of titanium per hour) and the amounts of destroying agent used for two ratios Al/Ti, one of these ratios being 1 and the other being 5.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Polymerisation Methods In General (AREA)
US05/661,414 1975-02-28 1976-02-25 Deactivation of catalysts of the ziegler type used for the preparation of polyethylene in high pressure, high temperature processes Expired - Lifetime US4105609A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR7506436 1975-02-28
FR7506436A FR2302305A1 (fr) 1975-02-28 1975-02-28 Procede perfectionne de polymerisation et de copolyme

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US4105609A true US4105609A (en) 1978-08-08

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US (1) US4105609A (OSRAM)
JP (1) JPS5936641B2 (OSRAM)
BE (1) BE838992A (OSRAM)
BR (1) BR7601217A (OSRAM)
CA (1) CA1070898A (OSRAM)
DE (1) DE2607601C2 (OSRAM)
DK (1) DK144948C (OSRAM)
FR (1) FR2302305A1 (OSRAM)
GB (1) GB1535568A (OSRAM)
IE (1) IE42642B1 (OSRAM)
IT (1) IT1057639B (OSRAM)
LU (1) LU74422A1 (OSRAM)
NL (1) NL7602132A (OSRAM)

Cited By (48)

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US4342853A (en) * 1979-07-05 1982-08-03 Societe Chimique Des Charbonnages--Cdf Chimie Process for manufacturing ethylene polymers
EP0062127A1 (en) * 1980-12-11 1982-10-13 Du Pont Canada Inc. Deactivation of catalyst in solution process for polymerization of alpha-olefins
DE3322329A1 (de) * 1982-06-24 1983-12-29 Mitsubishi Petrochemical Co., Ltd., Tokyo Verfahren zur herstellung von polyethylen
US4425464A (en) 1982-05-20 1984-01-10 The Dow Chemical Company Neutralizing polyethylene catalyst residues
US4525546A (en) * 1982-11-29 1985-06-25 Asahi Kasei Kogyo Kabushiki Kaisha Process for producing polyethylene and an ethylene-α-olefin copolymer
EP0148302A1 (en) * 1984-01-10 1985-07-17 The Dow Chemical Company Neutralizing polyethylene catalyst residues
US4551509A (en) * 1982-07-29 1985-11-05 Societe Chimique Des Charbonnages S.A. Process for manufacturing homopolymers and copolymers of ethylene
US4558105A (en) * 1983-12-07 1985-12-10 Chemplex Company Copolymerization of ethylene
US4634744A (en) * 1985-01-09 1987-01-06 Chemplex Company Method of catalyst deactivation
US4650841A (en) * 1982-12-24 1987-03-17 Societe Chimique des Chabonnages Continuous process for the manufacture of ethylene homopolymers or ethylene copolymers
WO1987003603A1 (en) * 1985-12-16 1987-06-18 Exxon Research And Engineering Company End-capped polymer chains, graft and star copolymers, and process of making same
US4755572A (en) * 1982-12-24 1988-07-05 Societe Chimique Des Charbonnages S.A. Process for the manufacture of homopolymers or copolymers of ethylene
US4786717A (en) * 1986-11-10 1988-11-22 Aristech Chemical Corporation Deactivation of aluminum alkyls
US4818799A (en) * 1987-11-13 1989-04-04 Shell Oil Company Process for the in-reactor stabilization of polyolefins
US4900792A (en) * 1983-06-13 1990-02-13 Allied-Signal Inc. Crosslinkable polyethylene composition
US5030695A (en) * 1983-06-15 1991-07-09 Exxon Research & Engineering Company End-capped polymer chains, star and graft copolymers, and process of making same
US6022916A (en) * 1993-03-29 2000-02-08 General Electric Company Processing stabilizer formulations
US6180730B1 (en) * 1998-01-21 2001-01-30 Nova Chemicals (International) S.A. Catalyst deactivation
US20090062465A1 (en) * 2007-08-27 2009-03-05 Nova Chemicals (International) S.A. Process for high temperature solution polymerization
US20090062495A1 (en) * 2007-08-27 2009-03-05 Nova Chemicals (International) S.A. High temperature process for solution polymerization
US20110144254A1 (en) * 2007-08-27 2011-06-16 Nova Chemicals (International) S.A. Process for high temperature solution polymerization
US20130341567A1 (en) * 2011-03-08 2013-12-26 Dow Global Technologies Llc Process for Recycling Solvent Used in an Ethylene-Based Polymerization Reaction and System Therefor
WO2015040522A1 (en) 2013-09-19 2015-03-26 Nova Chemicals (International) S.A. A solution polymerization process with improved energy utilization
WO2016063200A1 (en) 2014-10-21 2016-04-28 Nova Chemicals (International) S.A. Continuous solution polymerization process
WO2016063205A2 (en) 2014-10-21 2016-04-28 Nova Chemicals (International) S.A. Dilution index
WO2016063164A2 (en) 2014-10-21 2016-04-28 Nova Chemicals (International) S.A. Solution polymerization process
US9428597B2 (en) 2013-03-15 2016-08-30 Nova Chemicals (International) S.A. Solution polymerization processes with reduced energy usage
WO2017013509A1 (en) 2015-07-17 2017-01-26 Nova Chemicals (International) S.A. Shrink films
WO2018146649A1 (en) 2017-02-13 2018-08-16 Nova Chemicals (International) S.A. Caps and closures
WO2018193328A1 (en) 2017-04-19 2018-10-25 Nova Chemicals (International) S.A. Multi reactor solution polymerization, polyethylene and polyethylene film
WO2018193327A1 (en) 2017-04-19 2018-10-25 Nova Chemicals (International) S.A. Multi reactor solution polymerization
WO2018193331A1 (en) 2017-04-19 2018-10-25 Nova Chemicals (International) S.A. Means for increasing the molecular weight and decreasing the density of ethylene interpolymers employing mixed homogeneous catalyst formulations
WO2018193375A1 (en) 2017-04-19 2018-10-25 Nova Chemicals (International) S.A. Means for increasing the molecular weight and decreasing the density of ethylene interpolymers employing homogeneous and heterogeneous catalyst formulations
WO2019086987A1 (en) 2017-11-06 2019-05-09 Nova Chemicals (International) S.A. Polyolefin preparation process
WO2019092524A1 (en) 2017-11-07 2019-05-16 Nova Chemicals (International) S.A. Ethylene interpolymer products and films
WO2019092525A1 (en) 2017-11-07 2019-05-16 Nova Chemicals (International) S.A. An improved process to manufacture ethylene interpolymer products
WO2019092523A1 (en) 2017-11-07 2019-05-16 Nova Chemicals (International) S.A. Manufacturing ethylene interpolymer products at higher production rate
WO2019099138A1 (en) 2017-11-17 2019-05-23 Exxonmobil Chemical Patents Inc. Method of online cleaning of heater exchangers
WO2019123096A1 (en) 2017-12-18 2019-06-27 Nova Chemicals (International) S.A. Solution polymerization process
WO2019190949A1 (en) * 2018-03-28 2019-10-03 Dow Global Technologies Llc Ziegler-natta catalyst deactivation and neutralization
WO2020144571A1 (en) 2019-01-09 2020-07-16 Nova Chemicals (International) S.A. Ethylene interpolymer products having intermediate branching
WO2021084416A1 (en) 2019-11-01 2021-05-06 Nova Chemicals (International) S.A. Linear high-density polyethylene with high toughness and high escr
WO2021191814A2 (en) 2020-03-26 2021-09-30 Nova Chemicals (International) S.A. Nonlinear rheology of ethylene interpolymer compositions
WO2021224847A1 (en) 2020-05-08 2021-11-11 Nova Chemicals (International) S.A. Ethylene interpolymer products having unique melt flow-intrinsic viscosity (mfivi) and low unsaturation
WO2021224846A1 (en) 2020-05-08 2021-11-11 Nova Chemicals (International) S.A. Ethylene interpolymer products having unique melt flow-intrinsic viscosity (mfivi) and high unsaturation
WO2022043785A1 (en) 2020-08-26 2022-03-03 Nova Chemicals (International) S.A. Ethylene interpolymer products having a melt flow-intrinsic viscosity index (mfivi)
CN115210268A (zh) * 2020-03-24 2022-10-18 巴塞尔聚烯烃股份有限公司 制备乙烯聚合物的悬浮工艺，包括悬浮介质的后处理
WO2024235431A1 (en) 2023-05-12 2024-11-21 Nova Chemicals (International) S.A. Solution-phase polymerization process

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AU548257B2 (en) * 1981-06-09 1985-12-05 Du Pont Canada Inc. Deactivation of alpha olefin catalyst
DE3211457A1 (de) * 1982-03-27 1983-09-29 Ruhrchemie Ag, 4200 Oberhausen Kontinuierliches verfahren zur polymerisation und copolymerisation von ethylen
FR2538398B1 (fr) * 1982-12-24 1986-01-24 Charbonnages Ste Chimique Procede continu ameliore de fabrication d'homopolymeres ou de copolymeres de l'ethylene
DE3305782A1 (de) * 1983-02-19 1984-08-30 Ruhrchemie Ag, 4200 Oberhausen Verfahren zur polymerisation und copolymerisation von ethylen
JPS604509A (ja) * 1983-06-21 1985-01-11 Ube Ind Ltd エチレンの重合法
DE3335824A1 (de) * 1983-10-01 1985-04-18 Ruhrchemie Ag, 4200 Oberhausen Verfahren zur polymerisation und copolymerisation von ethylen
DE3415527A1 (de) * 1984-04-26 1985-10-31 Ruhrchemie Ag, 4200 Oberhausen Verfahren zur polymerisation und copolymerisation von ethylen
EP4431583A1 (fr) 2023-03-14 2024-09-18 SNF Group Methode d'injection d'une solution aqueuse de polymere dans une formation souterraine

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Cited By (68)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4342853A (en) * 1979-07-05 1982-08-03 Societe Chimique Des Charbonnages--Cdf Chimie Process for manufacturing ethylene polymers
US4430488A (en) 1980-12-11 1984-02-07 Du Pont Canada Inc. Deactivation of catalyst in solution process for polymerization of α-o
EP0062127A1 (en) * 1980-12-11 1982-10-13 Du Pont Canada Inc. Deactivation of catalyst in solution process for polymerization of alpha-olefins
US4425464A (en) 1982-05-20 1984-01-10 The Dow Chemical Company Neutralizing polyethylene catalyst residues
US4719270A (en) * 1982-06-24 1988-01-12 Mitsubishi Petrochemical Company Limited Process for production of polyethylene
US5086131A (en) * 1982-06-24 1992-02-04 Mitsubishi Petrochemical Company Limited Process for production of polyethylene
DE3322329A1 (de) * 1982-06-24 1983-12-29 Mitsubishi Petrochemical Co., Ltd., Tokyo Verfahren zur herstellung von polyethylen
US4551509A (en) * 1982-07-29 1985-11-05 Societe Chimique Des Charbonnages S.A. Process for manufacturing homopolymers and copolymers of ethylene
US4525546A (en) * 1982-11-29 1985-06-25 Asahi Kasei Kogyo Kabushiki Kaisha Process for producing polyethylene and an ethylene-α-olefin copolymer
US4755572A (en) * 1982-12-24 1988-07-05 Societe Chimique Des Charbonnages S.A. Process for the manufacture of homopolymers or copolymers of ethylene
US4650841A (en) * 1982-12-24 1987-03-17 Societe Chimique des Chabonnages Continuous process for the manufacture of ethylene homopolymers or ethylene copolymers
US4900792A (en) * 1983-06-13 1990-02-13 Allied-Signal Inc. Crosslinkable polyethylene composition
US5030695A (en) * 1983-06-15 1991-07-09 Exxon Research & Engineering Company End-capped polymer chains, star and graft copolymers, and process of making same
US4558105A (en) * 1983-12-07 1985-12-10 Chemplex Company Copolymerization of ethylene
EP0148302A1 (en) * 1984-01-10 1985-07-17 The Dow Chemical Company Neutralizing polyethylene catalyst residues
US4634744A (en) * 1985-01-09 1987-01-06 Chemplex Company Method of catalyst deactivation
EP0191220B1 (en) * 1985-01-09 1991-04-24 Quantum Chemical Corporation Method of deactivating ethylene polymerisation catalysts
WO1987003603A1 (en) * 1985-12-16 1987-06-18 Exxon Research And Engineering Company End-capped polymer chains, graft and star copolymers, and process of making same
US4786717A (en) * 1986-11-10 1988-11-22 Aristech Chemical Corporation Deactivation of aluminum alkyls
US4818799A (en) * 1987-11-13 1989-04-04 Shell Oil Company Process for the in-reactor stabilization of polyolefins
US6022916A (en) * 1993-03-29 2000-02-08 General Electric Company Processing stabilizer formulations
US6180730B1 (en) * 1998-01-21 2001-01-30 Nova Chemicals (International) S.A. Catalyst deactivation
US20090062465A1 (en) * 2007-08-27 2009-03-05 Nova Chemicals (International) S.A. Process for high temperature solution polymerization
US20090062495A1 (en) * 2007-08-27 2009-03-05 Nova Chemicals (International) S.A. High temperature process for solution polymerization
US7650930B2 (en) 2007-08-27 2010-01-26 Nova Chemical (International) S.A. High temperature process for solution polymerization
US7919568B2 (en) 2007-08-27 2011-04-05 Nova Chemicals (International) S.A. Process for high temperature solution polymerization
US20110144254A1 (en) * 2007-08-27 2011-06-16 Nova Chemicals (International) S.A. Process for high temperature solution polymerization
US8431096B2 (en) 2007-08-27 2013-04-30 Nova Chemicals (International) S.A Process for high temperature solution polymerization
US20130341567A1 (en) * 2011-03-08 2013-12-26 Dow Global Technologies Llc Process for Recycling Solvent Used in an Ethylene-Based Polymerization Reaction and System Therefor
US9708418B2 (en) * 2011-03-08 2017-07-18 Dow Global Technologies Llc Process for recycling solvent used in an ethylene-based polymerization reaction and system therefor
US9428597B2 (en) 2013-03-15 2016-08-30 Nova Chemicals (International) S.A. Solution polymerization processes with reduced energy usage
US9574025B2 (en) 2013-09-19 2017-02-21 Nova Chemicals (International) S.A. Solution polymerization process with improved energy utilization
WO2015040522A1 (en) 2013-09-19 2015-03-26 Nova Chemicals (International) S.A. A solution polymerization process with improved energy utilization
WO2016063164A2 (en) 2014-10-21 2016-04-28 Nova Chemicals (International) S.A. Solution polymerization process
WO2016063205A2 (en) 2014-10-21 2016-04-28 Nova Chemicals (International) S.A. Dilution index
WO2016063200A1 (en) 2014-10-21 2016-04-28 Nova Chemicals (International) S.A. Continuous solution polymerization process
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DK144948C (da) 1982-11-29
CA1070898A (en) 1980-01-29
NL7602132A (nl) 1976-08-31
GB1535568A (en) 1978-12-13
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JPS5936641B2 (ja) 1984-09-05
LU74422A1 (OSRAM) 1976-08-13
DK81776A (da) 1976-08-29
FR2302305A1 (fr) 1976-09-24
IT1057639B (it) 1982-03-30
IE42642B1 (en) 1980-09-24
BR7601217A (pt) 1976-09-14
IE42642L (en) 1976-08-28
DE2607601C2 (de) 1984-09-13
DK144948B (da) 1982-07-12
BE838992A (fr) 1976-06-16
DE2607601A1 (de) 1976-09-09
FR2302305B1 (OSRAM) 1978-12-29

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